Polynitro diamines



United States Patent 3,029,285 POLYNITRO DIAMINES Milton B. Frankel, Pasadena, and Karl Klager. Sacramento, C'alif., assignors to Aerojet-General Corporation, Azusa, Calif., a corporation of Ohio No Drawing. Filed Nov. 18, 1957, Ser. No. 698,888 18 Claims. (Cl. 260-583) This invention relates to new compositions of matter and a method for their preparation. In particular, this invention relates to polynitro diamines having the general formula:

wherein A is an alkylene radical and R is a hydrogen, nitro, or alkyl radical.

The nitro compounds of this invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket or the'like, as the main explosive charge. An example of such a missile is dis closed in US. Patent No. 2,470,162, issued May 17, 1949. One way of using thehigh explosives in a device such as that disclosed in US. Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufiiciently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.

In addition to being useful as high explosives themselves, the compounds of this invention, such as l,1,1,6,6,11,l 1,1 l-octanitro-3,9-diaza undecane, react with nitric acid to form other high explosive compounds, such as 1,1,1,3,6,6,9,11,11,1l-decanitro-3,9-diaza undecane, as more fully disclosed in our copending US. patent application Ser. No. 644,694, filed March 7, 1957, now US. Patent No. 2,978,510.

The compounds of this invention are prepared by the condensation of ,8-geminal dinitro alcohols with polynitro diamines, in accordance with the general reaction scheme set forth below:

I N02 N07 NO: NO: NO:

EXAMPLE I Preparation of I,Z,1,6,6,11,11,11-Ocumitr0-3,9- Diuza Undecane A solution of 26.5 gm. (0.1 mole) of 3,3-dinitro-l,5- pentane diamine dihydrochloride, 36.2 gm. (0.2 mole) of trinitroethanol and 100 ml. of water was placed in a flask fitted with a mechanical stirrer. Sodium hydroxide in an ice amount of 0.20 mole was added and a yellow solid precipitated. The product was collected, washed with water and dried to yield 34 gm. of a yellow solid, M.P. 93-95 C., with decomposition. The explosive values of this compound are as follows:

Lead block value 143 T.N.T.=100 Ballistic mortar value 146 T.N.T.'=100 EXAMPLE II Preparation of 2,2,7,7,12,12-Hexanitr0-4,10-Diaza Tridecane 2,2,7,7,l2,12-hexanitro-4,lO-diaza tridecane was prepared by condensing 2,2-dinitropropanol with 3,3-dinitro- 1,5-pentane diamine in the manner described in Example I. The product was recovered in a quantitative yield and exhibited a MP. of 95100 C. The explosive values of this compound are as follows:

Lead block value 91 T.N.T.-= Ballistic mortar value T.N.T.=100

Optimum results were obtained when the reaction was conducted at a pH of less than about 8 and preferably from about 4 to about 8. As a matter of convenience, it is preferred to generate the starting diamine in situ. Usually a strong mineral acid salt of the amine is emloyed in the presence of a base such as the hydroxide or lower alkanoic acid salts of an alkali or alkaline earth metal, For reasons of convenience and economy we prefer to use sodium hydroxide as the diamine generating agent but other suitable agents such as calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium acetate, etc., can be used for this purpose if desired.

Any of the strong mineral acid salts, such as nitric acid, hydrochloric acid, etc., salts, of our diamine starting materials can be used in the practice of this invention. These salts are prepared by hydrolyzing a gem-dinitroalkane dicarbamate, such as dimethyl-3,3-dinitr0-1,5-pen tanedicarbamate, in the presence of a strong mineral acid to form the corresponding mineral acid salt, such as 3,3- dinitro-l,S-pentanediamine dihydrochloride, as more fully disclosed in assignees copending US. patent application Ser. No. 652,305 filed April 11, 1957.

The fl-gem-dinitro alcohols used as starting materials for this invention, such as 2,2,2-trinitroethanol, are prepared by condensing labile hydrogen containing nitroalkanes, such as trinitromethane, with formaldehyde.

Reaction temperature is not critical in the practice of this invention, the only effect of temperature variation being a corresponding increase or decrease in reaction rate.

It will be appreciated that a variety of polynitro diamines can be prepared according to the method of our invention. For example, 2,2-dinitropentanol and 2,2- dinitro-3-methylbutanol condense with 4,4-dinitro-l,7- heptane diamine as well as 3,3-dinitro-1,5-pentane diamine to yield condensation products, namely, 4,4,10,10,16,16- hexanitro-6,14-diaza nonadecane; 2,l6-dimethyl-3,3,9,9, 15,15-hexanitro-5,13-diaza heptadecane; 4,4,9,9,14,14- hexanitro-6,12-diaza heptadecane; and 2,14-dimethyl-3,3, 8,8,l3,l3-hexanitro-5,l1-diaza pentadecane. Also, 2,2- dinitroethanol condenses with 3,3-dinitro-1,6-hexane diamine to yield 1,1,6,6,l2,12-hexanitro-3,l0 diaza d0- decane. It is, of course, within the scope of our invention to employ mixtures of B-gem-dinitro alcohols for our condensation reaction.

It is apparent that any member of this series of aliphatic polynitro diamines may be prepared by merely selecting the appropriate polynitro diamine and condensing it with the desired fi-geminal dinitro alcohol, in accordance with the teachings of this invention.

This application is acontinuation-in-part of our co- 3 pending US. patent application Ser. No. 421,984, filed April 8, 1954, now abandoned.

We claim: 1. As compositions of matter, aliphatic polynitro diamines having the formula:

wherein A is a lower alkylene radical and R is a radical 10 selected from the group consisting of hydrogen, nitro, and lower alkyl radicals.

2. As compositions of matter, aliphatic polynitro diamines having the formula:

wherein A is a lower alkylene radical.

3. As compositions of matter, aliphatic polynitro diamines having the formula:

wherein A is a lower alkylene radical and R is a lower alkyl radical.

4. As compositions of matter, aliphatic polynitro diamines having the formula:

wherein A is a lower alkylene radical. 35 5. As a composition of matter, 2,2,7,7,12,12-hexanitro- 4,10-diaza tridecane having the structural formula:

6. As a composition of matter, 1,1,1,6,6,11,11,11-octanitro-3,9-diaza undecane having the structural formula:

7. As a composition of matter, 4,4,10,10,16,!6-hexanitro-6,14-diaza nonadecaue having the structural formula:

NO: NO:

11. As a composition of matter, 1,1,6,6,12,12-hexanitro'3,10-diaza dodecane having the structural formula:

12. The method of preparing aliphatic polynitro diamines having the formula:

which comprises condensing a S-geminal dinitro alcohol having the formula:

NO: R--( 1CHzOH N02 with a strong mineral acid salt of a polynitro primary diamine having the formula:

N O: NH -ACHa( )CHz-ANH;

wherein A is a lower alkyiene radical and R is a radical selected from the group consisting of hydrogen, nitro and 50 lower alkyl radicals, in the presence of a compound se- N01 N02 8. As a composition of matter, 2,16-dimethyl-3,3,9,9, 15,1 5hexanitro-5,13adiaza heptadecane having the structural formula:

OH: NO: NO:

9. As a composition of matter, 4,4,9,9,14,14-hexanitro- 6,12-diaza heptadecane having the structural formula:

NO: N02

N02 lected from the group consisting of the basic salts and lower alkanoic acid salts of the alkali and alkaline earth metals.

NO: CHs J-Crowns N0:

15. The method of preparing 2,2,7,7,12,12-hexanitro- 4,10-diaza tridecane which comprises condensing 2,2-di- N02 N01 10. As a composition of matter, 2,14-dimethyl- 3,3,8,8,13,13-hexanitro-5,1l-diaza pentadecane having the 7 structural formula:

CH NO; N02

nitorpropanol with 3,3-dinitro-l,5-pentane diamine dihyhydrochloride in the presence of sodium hydroxide.

16. The method of preparing 1,1,1,6,6,11,11,11-octanitro-3,9-diaza undecaue which comprises condensing 3,029,285 5 6 2,2,2-trim'troethanol with 3,3-dinitro-1,5-pentane diamine dihydrochloride in the presence of sodium hydroxide.

17. The method of preparing 1,1,6,6,12,12-hexanitro- 6,14-diaza nonadecane which comprises condensing 2,2- dinitropentanol with 4,4-dinitr0-1,7-hepiane diamine.

3,10-diaza dodecane which comprises condensing 2,2-di- References Cited m the file of tms Patent nitroethanol with 3,3-dinitro-L6-hexane diamine. 5 UNITED STATES PATENTS 18. The method of preparing 4,4,10,10,16,16-hexaz1itro- 2,731,460 Schenck et a1. Jan. 17, 1956 

1. AS COMPOSITION OF MATTER, ALIPHATIC POLYNITRO DIAMINES HAVING THE FORMULA: 